Blown corn stillage oil

ABSTRACT

Blown corn stillage oils and methods for making blown corn stillage oils are disclosed. In one aspect the corn stillage oils are stripped to reduce the acid value of the resulting blown, stripped corn stillage oil. The method includes heating a corn stillage oil to a temperature of at least 90° C., and passing air through the heated oil to produce a blown corn stillage oil having a viscosity of at least 50 cSt at 40° C. In one aspect, the blown corn stillage oil is stripped to reduce the acid value of the blown, stripped corn stillage oil to 5 mg KOH/gram or less.

CROSS REFERENCE TO RELATED APPLICATION

This application is a national stage entry of International PatentApplication No. PCT/US2010/35759, filed 21 May 2010, entitled BLOWN CORNSTILLAGE OIL, which application claims the benefit of U.S. ProvisionalPatent Application No. 61/180,664, filed 22 May 2009, entitled BLOWNCORN STILLAGE OIL, which applications are hereby incorporated byreference in their entirety.

FIELD

The present disclosure relates to blown corn stillage oil and in someaspects blown, stripped corn stillage oils. The disclosure also relatesto methods for making such oils

BACKGROUND

Ethanol production from corn has increased in recent years. The corn istypically ground to a course powder that is then mixed with water andyeast and fermented to produce a fermented mixture (sometimes referredto as “mash”) that contains residual solids, ethanol and other liquids.The other liquids include water, monoglycerides, diglycerides,triglycerides, glycerin, and free fatty acids. Typically, the liquidportion of the mash is heated to distill off the ethanol, which iscaptured and sold as an additive for automotive fuels.

The residual liquid remaining after the ethanol is removed contains freefatty acids and glycerol, and from 1% to 3% by weight monoglycerides,diglycerids, triglycerides. The residual liquid from the distillationhas generally been sold together with the solids portion of the mash as“distillers dry grain.” The distillers dry grain generally is used asfeed for livestock.

SUMMARY

The inventors have surprisingly discovered that the monoglycerides,diglycerides, triglycerides, free fatty acids, and glycerol (hereinaftercollectively referred to as “corn stillage oil”) can be recovered fromthe other residual liquids of the distillation process by suitablemeans, preferably by centrifugation of the residual material remainingafter the ethanol has been distilled off. Centrifugation typicallyrecovers twenty five percent of the corn stillage oil originally presentin the residual material being centrifuged.

The corn stillage oil recovered by centrifugation typically: has an acidvalue from 16 to 32 mg KOH/gram, preferably from 18 to 30 mg KOH/gram;has an iodine value from 110 to 120 g I₂/100 g sample; and contains from0.05 to 0.29 percent by weight monoglycerides, from 1.65-7.08 percent byweight diglycerides, from 70.00 to 86.84 percent by weighttriglycerides, from 8 to 16 percent by weight (for example, from 9 to 15percent by weight) free fatty acids, and from 0.00 to 0.20 weightpercent glycerin. Typically, the corn stillage oil has from 53 to 55percent by weight groups derived from diunsaturated fatty acids, from 39to 43 percent by weight groups derived from monounsaturated fatty acids,from 15 to 18 percent by weight groups derived from saturated fattyacids, and from 1 to 2 percent by weight groups derived fromtriunsaturated fatty acids. The groups derived from each of the abovefatty acids are present either as groups within the mono-, di-, andtri-glycerides or as free fatty acids.

The free fatty acid content of the corn stillage oil is very highcompared to conventional vegetable oils. Surprisingly, the inventorshave discovered processes that can be readily used to process the highfatty acid containing stillage oil to provide beneficial products.

One inventive method to process the corn stillage oil is to heat the oilto a temperature of at least 90° C., typically from 90° C. to 125° C.,preferably from 100° C. to 120° C., and more preferably from 105° C. to115° C. and pass air through it (commonly referred to as “sparging”) fora desired period of time. This process polymerizes the components of thecorn stillage oil and introduces hydroxyl, epoxy functionality and etherlinkages. The resulting blown-corn stillage oil can be further processedin order to provide final oil products that can be used in variousend-use applications.

In one preferred aspect, the blown-corn stillage oil is stripped toreduce its free fatty acid content and to remove other volatiles fromthe oil.

In a particularly preferred aspect, the corn stillage oil is blown for asufficient period of time at an appropriate temperature to producehighly polymerized oil. For example, air is blown (sparged through) thecorn stillage oil being maintained at a temperature of from 90° C. to125° C. (preferably from 100° to 120° C. and more preferably from 105°C. to 115° C.) typically for from 2 to 20 hours (preferably from 3 to 18hours). The resulting polymerized oil is then relatively heavilystripped. For example, the blown oil is heated to a temperature from230° C. to 270° C. (preferably from 240° to 260° C.), and in someinstances from 235° C. to 245° C., and vacuum stripped at a pressure of100 torr or less, preferably 75 torr or less, and more preferably 50torr or less and not preferably 20 torr or less for typically from 8 to12 hours (preferably from 9 to 11 hours). This stripping reduces thecontent of free fatty acids and other volatiles such as lower molecularweight glycerides and unexpectedly produces a stripped, blown-cornstillage oil having a very high flash point that can be used for end-useapplications such as very high temperature suitable de-dusting fluids.The stripping also typically “Bodies” the oil and further increases itsmolecular weight and viscosity. “De-dusting fluids” are fluids used forreducing the dust created when a surface is agitated or perturbed. Thestripped, blown-corn stillage oil will help minimize the chances ofsparking and/or explosions in high flash point environments and willalso degrade slower than petroleum based mineral oils having lower flashpoints. Typically, this oil has a flash point of at least 300° C.,preferably at least 310° C., and more preferably at least 320° C.

In another particularly preferred aspect, the corn stillage oil is blownfor a relatively shorter period of time to produce an oil that islightly polymerized. For example, air is blown (sparged through) thecorn stillage oil being maintained at a temperature of from 90° C. to125° C. (preferably from 100° to 120° C., and more preferably from 105°to 115° C.) typically for from 2 to 10 hours (preferably from 3 to 8hours). The lightly polymerized oil is then relatively heavily strippedto reduce the content of free fatty acids and other volatiles within theoil. For example, the blown oil is heated to a temperature from 230° C.to 270° C. (preferably from 240° to 260° C.) and vacuum stripped at apressure of 100 torr or less, preferably 75 torr or less, and morepreferably 50 torr or less typically for from 8 to 12 hours (preferablyfrom 9 to 11 hours). This stripped, blown-corn stillage oil has anunexpectedly low pour point, typically less than −14° C. This low pourpoint oil is particularly useful for low temperature de-dustapplications and for use in Bar & Chain lubricant end-use applications.Examples of end-use applications include many areas where petroleumbased oils are used such as: chain saw lubricant applications and otherapplications that utilize bar, chain, and sprockets that demand mediumviscosity oils to provide adequate lubrication. This blown and strippedoil can also be used in metal forming operations such as drawing, inhydraulic systems as a base fluid and in 2 cycle engine oilformulations. Examples of de-dust applications where relatively low pourpoints oils as described here are useful include: fertilizer plantswhere fertilizer is transferred outdoors in winter temperatures and rockcrushing applications where dust is a concern. If a lower pour point isdesired, additives such as a heavily blown linseed oil (such as theblown linseed oil available from Cargill, Incorporated under thetrademark VOM 25), or diesters having a crystallization temperature lessthan −28.9° C., preferably less than −34° C., more preferably less than−40° C. and further more preferably less than −45° C. and in someinstances less than −54° C. (such as bis (2-ethylhexyl) adipate) can beblended with the low pour point oil to produce a very low pour point oilhaving a pour point typically less than −23° C. and preferably less than−26° C.

Surprisingly, the inventor has discovered that a titre (as describedbelow) typically is reduced to less than one percent by weight (1 wt %)by heating the corn stillage oil during the blowing.

DETAILED DESCRIPTION

“Flash Point” or “Flash Point Temperature” is a measure of the minimumtemperature at which a material will initially flash with a brief flame.It is measured according to the method of ASTM D-92 using a ClevelandOpen Cup and is reported in degrees Celsius (° C.).

“Pour Point” or “Pour Point Temperature” is a measure of the lowesttemperature at which a fluid will flow. It is measured according to themethod of ASTM D-97 and is reported in degrees Celsius (° C.).

“Iodine Value” (IV) is defined as the number of grams of iodine thatwill react with 100 grams of material being measure. Iodine value is ameasure of the unsaturation (carbon-carbon double bonds andcarbon-carbon triple bonds) present in a material. Iodine Value isreported in units of grams iodine (I₂) per 100 grams material and isdetermined using the procedure of AOCS Cd Id-92.

“Hydroxyl number” (OH#) is a measure of the hydroxyl (—OH) groupspresent in a material. It is reported in units of mg KOH/gram materialand is measured according to the procedure of ASTM E1899-02.

“Acid Value” (AV) is a measure of the residual hydronium groups presentin a compound and is reported in units of mg KOH/gram material. The acidnumber is measured according to the method of AOCS Cd 3d-63.

“Gardner Color Value” is a visual measure of the color of a material. Itis determined according to the procedure of ASTM D1544, “Standard TestMethod for Color of Transparent Liquids (Gardner Color Scale)”. TheGardner Color scale ranges from colors of water-white to dark browndefined by a series of standards ranging from colorless to dark brown,against which the sample of interest is compared. Values range from 0for the lightest to 18 for the darkest. For the purposes of theinvention, the Gardner Color Value is measured on a sample of materialat a temperature of 25° C.

Recovery of Corn Stillage Oil

Fermented mash comprising ethanol, water, residual grain solids(including proteins, fats, and unfermented sugars and carbohydrates),and from 1 to 3 percent by weight corn stillage oil is heated to distilland recover ethanol from the fermented mash. Typically, the ethanol isdistilled by two methods.

In the first method, the fermented mash is heated to temperaturestypically from 76° C. to 99° C. under vacuum typically from 50 to 300torr (for example from 150 to 250 torr) to distill off the desiredethanol. An example of this first method is the ethanol distillationprocess available from ICM, Incorporated (hereinafter the “ICMProcess”).

In the second method, the fermented mash is heated to temperaturestypically from 235° F. to 250° F. under pressures typically from 1 to 25psig (for example from 1 to 15 psig) to distill off the desired ethanol.An example of this second method is the process available from Delta-TCorporation (hereinafter the “Delta-T Process”).

For both the first and second method, after the ethanol is distilledoff, the remaining liquid portion typically contains from 1 wt % to 4 wt% corn stillage oil. The material remaining after the ethanol isdistilled off is typically centrifuged using a centrifuge, such as aWestfalia sliding disk centrifuge available from Westfalia Corporation.From 25 wt % to 35 wt % of the corn stillage oil contained in thematerial is recovered during this centrifugation step. The recoveredunprocessed corn stillage oil typically exhibits a Gardner color of 12or greater, for example, a Gardner color of from 14 to 18.

Corn stillage oil produced from the residual material of the firstdistillation method is hereinafter referred to as “vacuum distilled cornstillage oil.” Corn stillage oil produced from the residual material ofthe second distillation method is hereinafter referred to as “pressuredistilled corn stillage oil.” When the corn stillage oil is lightlyblown and not stripped, vacuum distilled corn stillage oil is preferablyutilized since the resulting blown corn stillage oil will have a lowervalue for Gardner color than a blown stillage oil made using a pressuredistilled corn stillage oil.

Unprocessed corn stillage oil typically exhibits: a viscosity at 40° C.of from 25 to 35 cSt (for example from 28 to 31 cSt) as measuredutilizing viscosity tubes in a constant temperature bath as furtherdescribed below; a viscosity at 100° C. of from 5 to 10 cSt for examplefrom 6 to 9 cSt as measured utilizing viscosity tubes in a constanttemperature bath as further described below; a Viscosity Index of from80 to 236 determined using the procedures and measurement scaleestablished by the Society of Automotive Engineers; a flash point from220° C. to 245° C., for example from 225° C. to 240° C.; asaponification value of from 170 to 206 mg KOH/g; a pour point typicallyof from −5° C. to −14° C.; an acid value of from 15 to 33 mg KOH/gram(for example, from 16 to 32 mg KOH/gram); an iodine value from 110 to125 grams I₂/100 grams sample; and from 8 to 16 wt % (for example, from9 to 15 wt %) free fatty acids.

Viscosity for this invention is measured according to the method of ASTMD445. In this method oil to be tested is placed in a calibrated glasscapillary viscometer, which is then placed into a constant temperaturebath at the temperature specified. Once thermal equilibrium is reached,the oil is drawn up into the reservoir of the capillary tube. As thefluid drains, it passes the top mark on the tube and a timer is started.When the oil passes the lower mark, the timer is stopped and the flowtime is recorded. The recorded flow time is multiplied by a factor whichis specific to each viscometer tube. The resultant product of the flowtime multiplied by the factor is reported as viscosity in cSt at thetest temperature.

Unprocessed corn stillage oil also typically contains two phases at 25°C. The first phase is the liquid phase, which settles toward the top ofany container that contains the corn stillage oil. This phase typicallyis reddish in color. The second phase is a solid that typically settlestoward the bottom of any container containing the oil. At 62° C., thesecond phase tends to dissolve into the liquid phase, but will settleout again if the untreated corn stillage oil is cooled to roomtemperature. The inventors have determined that the second solid phasetypically makes up at least 4 percent by weight (4 wt %) of the totalunprocessed corn stillage oil. For example, the second solid phase maymake up from 5 wt % to 12 wt % of the unprocessed corn stillage oil. Forpurposes of this invention, this second solid phase is referred to asthe “titre.”

Blowing the Corn Stillage Oil

The blowing typically is achieved by sparging air through corn stillageoil heated to from 90° C. to 125° C., preferably from 100° C. to 120°C., and more preferably from 105° C. to 115° C. The vessel containingthe corn stillage oil during the blowing step typically is atatmospheric pressure. The pressure of the air being sparged through theoil is generally high enough to achieve the desired air flow through thecorn stillage oil. The air is introduced at a sufficient flow rate for asufficient period of time to achieve the desired viscosity. Typically,the air is introduced into the corn stillage oil at a rate of 0.009 to0.011 cubic feet per minute per pound of corn stillage oil present.Preferably, the air is dispersed evenly in the vessel to maximizesurface area exposure. Typically the vessel will have a distributionring or spoke-like header to create small volume bubbles evenly withinthe oil. The duration of sparging air through the corn stillage oil isvaried and determined according to the desired properties of the blownoil and the end-use applications for the resulting product.

Surprisingly, the inventors have discovered that the corn stillage oildescribed above, can be effectively reacted with air to provideblown-corn stillage oil which advantageously has a relatively high levelof polymerization, as shown by their increased viscosities at 40° C. and100° C. (typically above 50 cSt @ 40° C. preferably above 60 cSt @ 40°C. more preferably above 130 cSt @ 40° C. and in some instances wherehigh molecular weight is particularly desirable, above 5000 cSt @ 40°C.; and (typically above 9 cSt @ 100° C., preferably above 11 cSt @ 100°C., more preferably above 12 cSt @ 100° C., and in some instances wherehigh molecular weight is particularly desirable, above 200 cSt @ 100° C.Typically, the blown corn stillage oils are not stripped of free fattyacids for applications where free fatty acids are a benefit. Forexample, for applications where boundary lubrication are important, theblown corn stillage oil preferably is not stripped as described below.

Surprisingly, the acid value for the blown corn stillage oil is notsignificantly increased compared to the acid value for the unblown cornstillage oil. Typically the acid value does not increase when cornstillage oil is blown. Preferably, the blown corn stillage oil comprisesrelatively no more than 20 relative percent more free fatty acids thanthe starting unblown corn stillage oil. Preferably, the blown cornstillage oil comprises relatively no more than 10 relative percent morefree fatty acids than the starting unblown corn stillage oil, and morepreferably, the free fatty acid content of the blown corn stillage oilis equivalent to the free fatty acid content of the starting cornstillage oil.

That the free fatty acid content of blown corn stillage oil is notsignificantly higher than the free fatty acid value for the startingunblown corn stillage oil, is unexpected as the acid value for othervegetable oils, such as soybean oil does increase significantly when theoil is blown. For example, a sample of soybean oil with an acid value ofless than 0.1 mg KOH/g when blown to a viscosity of 130 cSt @ 40° C.typically has an acid value of 9 to 11 mg KOH/gram, or more. Generally,the acid value of a vegetable oil increases significantly when air isblown into the oil at temperatures above 100° C. As the blown-cornstillage oil does not have significantly higher acid value than theunblown corn stillage oil, the blown corn stillage oil can beeffectively stripped of volatiles, such as free fatty acids, usingconventional stripping equipment and methods.

Generally, the acid value of a vegetable oil increases significantlywhen air is blown into the oil at temperatures above 100° C. As theblown-corn stillage oil does not have significantly higher acid valuethan the unblown corn stillage oil (i.e. acid value from 9 to 32 mgKOH/gram), the blown corn stillage oil can be effectively stripped ofvolatiles, such as free fatty acids, using conventional strippingequipment and methods.

The reactions that occur during the blowing of the oil increase themolecular weight of the oil, which tends to increase the viscosity ofthe blown oil versus the unblown oil. Additionally, the blowing processintroduces hydroxyl functionality onto the resulting oil, which alsotends to increase the viscosity of the oil. The blown-corn stillage oiltypically has a hydroxyl number from 8 to 60 mg KOH/gram oil. The higherviscosity (especially at higher temperature) provides the oil withbetter hydrodynamic lubrication properties.

The inventors also have surprisingly discovered that corn stillage oilcan be more readily blown to desired viscosities, such as 70 cSt, thansoybean oil under the same blowing conditions. For example, air wassparged through corn stillage oil and soybean oil maintained at 100° C.and atmospheric pressure to determine how long it would take each tobuild viscosity. As can be seen from Table 1, below, the blown cornstillage oil's viscosity increased much quicker and reached a viscosityof 70.9 cSt at 40° C. in 25.5 hours versus the blown soybean oil, whichtook 39.5 hours to reach a viscosity of 71.8 cSt at 40° C. under similarconditions. Therefore, it takes at least 20% less time for the blowncorn stillage oil to reach approximately 71 cSt at 40° C. than a blownsoybean oil to reach a similar viscosity, and in some instances at least25% less time, preferably at least 30% less time and more preferably atleast 35% less time for the blown corn stillage oil to reach a givenviscosity at 40° C. than a blown soybean oil under similar blowingconditions.

TABLE 1 Viscosity at 40° C. (cSt) TIME at 100° c. (Hrs) 0 1 2.25 3.256.25 11 12 13.25 16 16.75 19 21.25 23.5 25.5 32.5 39.5 blown, 33 33 3333 33 39.4 39.6 39.7 45.9 46.7 51.4 63.8 70.9 corn stillage oil Blown41.7 44.5 53.4 71.8 soybean oil

For high-flash point end-use applications (as described below) forexample, high temperature de-dust applications, asphalt viscosity indeximprovers and open gear lubricants applications, the blowing iscontinued for a time sufficient to obtain a blown corn stillage oilhaving a viscosity of: at least 450 cSt at 40° C., preferably at least500 cSt at 40° C.; and at least 50 cSt at 100° C., preferably at least55 cSt at 100° C., more preferably at least 70 cSt at 100° C., and insome applications at least 270 cSt @ 100 C. This will provide for an oilhaving a viscosity of: at least 500 cSt at 40° C., preferably at least700 cSt at 40° C., and more preferably at least 730 cSt at 40° C.; andat least 63 cSt at 100° C., preferably at least 68 cSt at 100° C., andmore preferably at least 70 cSt at 100° C. after stripping as described,below.

In an alternative aspect, the oil is blown to a lower viscosity, but isallowed to build more viscosity in during the stripping step describedbelow. In this alternative aspect, the blowing is continued for a timesufficient to obtain a blown oil blend having a viscosity of: at least200 cSt at 40° C., preferably at least 300 cSt at 40° C., and in someinstances at least 1500 cSt at 40° C. The blown oil is then stripped (asdescribed below) to sufficiently body the oil to provide a blown,stripped oil having a viscosity of at least 500 cSt at 40° C.,preferably at least 700 cSt at 40° C., and more preferably at least 730cSt at 40° C., and in some instances at least 5000 cSt at 40° C.

For large size reactors, for example reactors able to blow 45,000 poundsof oil, even with good dispersion and small volume air bubbles, it maytake longer (from 30 to 40 hours) to blow the oil to the desiredviscosity (when the oil is at a temperature of from 105° C. to 115° C.at atmospheric pressure, at the rates described above, to achieve thesedesired viscosities. Longer sparging times typically will be necessaryif the air is not evenly dispersed within the oil and/or the volume ofthe air bubbles are relatively larger.

For agricultural adjuvant use, de-dust fluids, metalworking oils, and asadditives to lower the softening point of asphalt the blowing iscontinued for a time sufficient to obtain a blown corn stillage oilhaving a viscosity of: at least 50 cSt at 40° C., preferably at least 60cSt at 40° C.; and at least 10 cSt at 100° C., preferably at least 13cSt at 100° C. This will provide an oil having a viscosity of at least50 cSt at 40° C., preferably at least 60 cSt at 40° C.; and at least 10cSt at 100° C., preferably at least 13 cSt at 100° C. With evendispersion and small volume air bubbles, air typically is spargedthrough the oil for from 2 to 8 hours (when the oil is at a temperatureof from 105° C. to 115° C. at atmospheric pressure, at the ratesdescribed above, to achieve these desired viscosities. Longer spargingtimes typically will be necessary if the air is not evenly dispersedwithin the oil and/or the volume of the air bubbles are relativelylarger. For large size reactors, for example reactors able to blow45,000 pounds of oil, even with good dispersion and small volume airbubbles, it may take longer (from 20 to 30 hours) to blow the oil to thedesired viscosity (when the oil is at a temperature of from 105° C. to115° C. at atmospheric pressure, at the rates described above, toachieve these desired viscosities. Longer sparging times typically willbe necessary if the air is not evenly dispersed within the oil and/orthe volume of the air bubbles are relatively larger.

For low pour point applications (as described below) the blowing iscontinued for a time sufficient to obtain a blown corn stillage oilhaving a viscosity of: at least 60 cSt at 40° C., preferably at least140 cSt at 40° C.; and at least 12 cSt at 100° C., preferably at least14 cSt at 100° C. This will provide an oil having a viscosity of atleast 60 cSt at 40° C., preferably at least 140 cSt at 40° C.; and atleast 12 cSt at 100° C., preferably at least 14 cSt at 100° C. The blowncorn stillage oil for these applications typically have a viscosity of:less than 500 cSt at 40° C., preferably less than 400 cSt at 40° C., andmore preferably less than 250 cSt at 40° c.; and less than 56 cSt at100° C., and preferably less than 43 cSt at 100° C., and more preferablyless than 29 cSt at 100° C. With even dispersion and small volume airbubbles, air typically is sparged through the oil for from 2 to 10hours, preferably from 3 to 8 hours (when the oil is at a temperature offrom 105° C. to 115° C. at atmospheric pressure, at the rates describedabove), to achieve these desired viscosities. Longer sparging timestypically will be necessary if the air is not evenly dispersed withinthe oil and/or the volume of the air bubbles are relatively larger. Forlarge size reactors, for example reactors able to blow 45,000 pounds ofoil, even with good dispersion and small volume air bubbles, it may takelonger (from 20 to 40 hours) to blow the oil to the desired viscosity(when the oil is at a temperature of from 105° C. to 115° C. atatmospheric pressure, at the rates described above, to achieve thesedesired viscosities. Longer sparging times typically will be necessaryif the air is not evenly dispersed within the oil and/or the volume ofthe air bubbles are relatively larger.

Optionally, a catalyst may be used in some embodiments to enhance theblowing of the oil. Examples of catalysts that may be useful includeperoxides, and catalysts comprising metals selected from the groupconsisting of Transition Elements and Group IV metals as described in“McGraw-Hill Dictionary of Scientific and Technical Terms,” Appendix 7(Fifth Edition 1994).

Further examples of catalysts that may be useful for enhancing theblowing procedure include catalysts comprising metals related from thegroup consisting of: tin, cobalt, iron, zirconium, titanium andcombinations thereof.

Stripping the Blown-Corn Stillage Oil

The blown-corn stillage oil is stripped by vacuum stripping. Thepressure during the stripping typically is less than 100 torr,preferably less than 75 torr, and more preferably 50 torr or less. Asmentioned above, the temperature during the stripping step typically isfrom 230° C. to 270° C., preferably from 240° C. to 260° C. Thestripping will lower the content of free fatty acids in the oil andtherefore reduce the acid value of the resulting stripped oil.Typically, the oil is sufficiently stripped to reduce the acid value ofthe resulting stripped blown-corn stillage oil to 5 mg KOH/g or less,preferably 4 mg KOH/g or less, and in some instances, such as where theoil is intended for high flash point end-use applications, less than 3.5mg KOH/g preferably less than 3.0 mg KOH/g and even more preferably 2.8mg KOH/g or less. Stripping the oil will also increase the viscosity ofthe resulting oil compared to the non-stripped oil and will increase theflash point of resulting oil. Typically, the oil is vacuum stripped fora period of from 8 to 12 hours, preferably from 9 to 11 hours. For largesize reactors, for example reactors able to strip 45,000 pounds of oil,it may take longer (from 20 to 60 hours) to strip the blown oil to theacid value (typically 5.0 mg KOH/gram or less, preferably 3.5 mgKOH/gram or less, and in some instances 3.0 mg KOH/gram or less andpreferably 2.8 mg KOH/gram or less. In an alternative embodiment, theinventors have surprisingly discovered that when it is necessary toreduce the acid value to particularly low levels (for example to valuesof 3.5 mg KOH/gram or less), it may be advantageous to optionally addsmall amounts of a polyol, such as glycerol, to the blown-corn stillageoil being stripped.

In a first preferred aspect of this alternative embodiment, theblown-corn stillage oil is stripped using nitrogen or vacuum strippinguntil the acid value of the oil is reduced to from 5 mg KOH/gram toabout 9 mg KOH/gram, preferably from about 7 mg KOH/gram to about 9 mgKOH/gram. Then a polyol, preferably glycerin is added to the oil and theoil is stripped until the acid value of the oil is less than 5.0,preferably until the acid value is 3.5 mg KOH/gram or less, and in someinstance 3.0 mg KOH/gram or less or 2.8 mg KOH/gram or less. During thisfinal stripping stage, a nitrogen purge preferably is maintained on theoil to assist in the removal of volatiles from the oil, including waterthat may be liberated by the reaction of glycerin with fatty acids.However, during this final stripping state a vacuum preferably is nolonger maintained on the vessel containing the oil. Once the acid valuehas been reduced to the desired value, the heat may be removed if thedesired viscosity has been obtained. If the desired viscosity has notbeen reached, the oil will continue to be heated until the desired valuefor viscosity is obtained. After the desired acid value and viscosityhave been obtained, the blown-corn stillage oil is allowed to cool. Inthis aspect the final hydroxyl number of the blown-corn stillage oil istypically less than 50 mg KOH/gram, preferably less than 40 mg KOH/gram,and in some instances less than 30 mg KOH/gram, for example from about23 to 29 mg KOH/gram. If a higher viscosity oil is desired, theviscosity of the blown-corn stillage oil typically is at least about 500cSt at 40° C., preferably at least 700 at 40° C., more preferably atleast 730 cSt at 40° C., and in some instances at least 5000 cSt at 40°C. If a relatively lightly polymerized oil is desired, the viscosity ofthe blown-corn stillage oil is from 60 cSt to 200 cSt at 40° C.

The amount of polyol added to the blown-corn stillage oil in this firstpreferred aspect typically is sufficient to obtain a ratio of moles ofhydroxyl groups added to fatty acid groups in the blown oil of fromabout 1:5 to less than about 1:1, preferably from about 1:4 to about9:10, more preferably from about 2:5 to about 4:5; and further morepreferably from 1:2 to 4:5.

In a second preferred aspect of this alternative embodiment, the polyolis added at the beginning or soon after stripping of the blown-cornstillage oil has commenced. In this second preferred aspect, thetemperature of the blown-corn stillage oil is as described above.Typically, sufficient polyol (preferably glycerin) is added to theblown-corn stillage oil to obtain a ratio of moles of hydroxyl groupsadded per mole of fatty acids groups present in the oil of from about1:1 to about 2:1, preferably from about 1.6:1 to about 1.9:1, and morepreferably from about 1.75:1 to about 1.85:1. During this aspect,nitrogen is sparged through the oil, typically at a rate of from about 5to 10 cfm per 45000 pounds mass oil. Preferably, during this aspect avacuum is not applied to the oil. Nitrogen is sparged through the oiluntil the acid value of the oil is less than 5 mg KOH/gram, preferablyless than 3.5 mg KOH/gram and in some instances 3.0 mg KOH/gram and even2.8 mg KOH/gram. Once the acid value has been reduced to the desiredvalue, the heat may be removed if the desired viscosity has beenobtained. If the desired viscosity has not been reached, the oil willcontinue to be heated until the desired value for viscosity is obtained.After the desired acid value and viscosity have been obtained, theblown-corn stillage oil is allowed to cool. If a higher viscosity oil isdesired, the viscosity of the blown-corn stillage oil typically is atleast about 500 cSt at 40° C., preferably at least 700 at 40° C., morepreferably at least 730 cSt at 40° C., and in some instances at least5000 cSt at 40° C. If a relatively lightly polymerized oil is desired,the viscosity of the blown-corn stillage oil is from 60 cSt to 200 cStat 40° C.

End-Use Applications Low Pour Point Applications

For end-use applications requiring low pour point temperatures, thestripped, blown-corn stillage oil typically exhibits a pour point oflower than −9° C., preferably lower than −10° C., and in some instances−14° C. or lower. Examples of end use applications where low pour pointis beneficial include, for example low temperature de-dust fluids (forexample, fertilizer plants where fertilizer is transferred outdoors inwinter temperatures and rock crushing applications where dust is aconcern), bar & chain lubricant fluids (such as, chain saw lubricantapplications and other applications that utilize bar, chain, andsprockets that demand medium viscosity oils to provide adequatelubrication), and asphalt softening point modifiers.

A stripped, blown-corn stillage oil formulation exhibiting even lowerpour point can be made by blending from 5 to 7 weight percent of aheavily blown linseed oil (such as the heavily blown linseed oilavailable from Cargill, Incorporated under the trade designation VOM25)or diesters having a crystallization temperature less than −28.9° C.,preferably less than −34° C., more preferably less than −40° C. andfurther more preferably less than −45° C. and in some instances lessthan −54° C. (such as bis (2-ethylhexyl) adipate). The pour point ofblown, stripped corn stillage oil blended with a heavily blown linseedoil and/or a diester as described above may have a pour point less than−23° C. and preferably less than −26° C. Preferably, both a blownlinseed oil and a diester, both as described above, are utilized tolower the pour point of the blown, stripped corn stillage oil. Theseoils are particularly useful for use in bar and chain lubricationend-use applications.

VOM25 has a viscosity of 44,000 cSt @ 40° C. and an acid value of ≦3milligram KOH/gram material.

For low pour point applications, the corn stillage oil typically isblown for a relatively shorter period of time to produce an oil that islightly polymerized. For example, air is blown (sparged through) thecorn stillage oil being maintained at a temperature of from 90° C. to125° C. (preferably from 100° to 120° C., and more preferably from 105°to 115° C.). typically for from 2 to 10 hours (preferably from 3 to 8hours). The lightly polymerized oil is then relatively heavily strippedto reduce the content of free fatty acids and other volatiles within theoil. For example, the blown oil is heated to a temperature from 230° C.to 270° C. (preferably from 240° to 260° C.) and vacuum stripped at apressure of 100 torr or less, preferably 75 torr or less, and morepreferably 50 torr or less typically for from 8 to 12 hours minutes(preferably from 9 to 11 hours).

This blown and stripped oil can also be used in metal forming operationssuch as drawing, in hydraulic systems as a base fluid and in 2 cycleengine oil formulations.

High-Flash Point Applications

High flash point applications often expose lubricating oil totemperatures above 500° F., often above 550° F. and in some instancetemperature up to and/or above 600° F. Petroleum-based oils generally donot have flash point temperatures high enough to safely operate in thistype of environments. Also, the petroleum-based oils may break down andrapidly oxidize and in a worse case scenario may burn in these types ofenvironments. The inventors have surprisingly found that by heavilyblowing the corn stillage oil its molecular weight and viscosity can beincreased sufficiently to be able to operate effectively in end-useapplications requiring such high flash points once the resulting blowncorn stillage oil has been stripped to reduce the acid value to 3.5 mgKOH/g or less, preferably 3.0 mg KOH/g or less, and more preferably 2.8mg KOH/g or less.

In a particularly preferred aspect, the corn stillage oil is blown for asufficient period of time at an appropriate temperature to producehighly polymerized oil. For example, air is blown (sparged through) thecorn stillage oil being maintained at a temperature of from 90° C. to125° C. (preferably from 100° to 120° C., and more preferably from 105°C. to 115° C.) typically for from 2 to 10 hours (preferably from 3 to 8hours). For large size reactors (for example reactors able to blow45,000 pounds of oil), the time period may be longer as described above.The resulting polymerized oil is then relatively heavily stripped. Forexample, the blown oil is heated to a temperature from 230° C. to 270°C. (preferably from 240° to 260° C.) and vacuum stripped at a pressureof 100 torr or less, preferably 75 torr or less, more preferably 50 torror less, and not preferably 20 tons or less for typically from 8 to 12hours (preferably from 9 to 11 hours). For large size reactors (forexample reactors able to strip 45,000 pounds of oil), the time periodmay be longer as described above. This stripping reduces the content offree fatty acids and other volatiles such as lower molecular weightglycerides and unexpectedly produces a stripped, blown-corn stillage oilhaving a very high flash point that can be used for end-use applicationssuch as very high temperature suitable de-dusting fluids. The stripped,blown-corn stillage oil will help minimize the chances of sparkingand/or explosions in high flash point environments and will also degradeslower than petroleum based mineral oils having lower flash points.Typically, the blown, stripped corn stillage oil for high-flash pointapplications has a flash point of at least 300° C., preferably at least310° C., and more preferably at least 320° C.

Typically, the high-flash point stripped, blown-corn stillage oiltypically exhibits a pour point of lower than 0° C., preferably lowerthan negative 5° C. This combination of high flash point and relativelylow pour point is unexpected and is believed to result from thestripped, blown corn stillage oil having a relatively narrow molecularweight distribution with completely randomized molecular structurescompared to petroleum base oils. This provides an oil that remainsflowable at relatively low temperatures, while still exhibiting goodviscosity and lubrication at high temperatures and a high flash point,as described above.

Examples of end-use applications that require such high flash pointsoils include, but are not limited to: asphalt modification end-useapplications and as high temperature de-dusting fluids utilized in hightemperature de-dust applications. “De-dusting fluids” are fluids usedfor reducing the dust created when a surface is agitated or perturbed.

EXAMPLES

The following examples are presented to illustrate the present inventionand to assist one of ordinary skill in making and using the same. Theexamples are not intended in any way to otherwise limit the scope of theinvention.

Example 1 Production of Vacuum Distilled Corn Stillage Oil

The vacuum distilled corn stillage oil of example 1 is made according tothe ICM Process. This process exposes the fermented corn mash totemperatures of about 82.2° C. under a vacuum from about 50 to about 300torr to distill off ethanol. The corn stillage oil is recovered bycentrifuging the materials remaining after the distillation to recoverthe vacuum distilled corn stillage oil. The properties of the vacuumdistilled corn stillage oil is set forth below in Table 2. While notmeasured, the vacuum distilled corn stillage oil is believed to containfrom about 5 to about 12 percent by weight titre.

TABLE 2 Properties of Vacuum Distilled Corn Stillage Oil Sample No. 2-140° C. Viscosity (cSt)  31 100° Viscosity (cSt)  8 Viscosity Index 249Flash Point (° C.) 238 Saponification Value (mg KOH/g) 202 Pour PointTemperature (° C.)   −7 Acid Value (mg KOH/grams)  22.2 Free Fatty Acid(wt %)  11.1 Iodine value (gram I₂/100 grams) 122 Gardner Color  15Hydroxyl number (mg KOH/gram)  9

Example 1a Production of Pressure Distilled Corn Stillage Oil

The pressure distilled corn stillage oil of example is is made accordingto the Delta T Process. In this process the fermented corn mash isexposed to temperatures of about 235° F. to 250° F. at pressures of fromabout 1 psig to about 15 psig to distill off ethanol. The pressuredistilled corn stillage oil is recovered by centrifuging the materialremaining after the distillation to recover the pressure distilled cornstillage oil. The properties of the pressure distilled corn stillage oilis set forth below in Table 2a. While not measured, the pressuredistilled corn stillage oil is believed to contain from about 5 to about12 percent by weight titre.

TABLE 2a Properties of Pressure Distilled Corn Stillage Oils Sample No.2-1a 40° C. Viscosity (cSt)  31 100° Viscosity (cSt)  8 Viscosity Index249 Flash Point (° C.) 238 Saponification Value (mg KOH/g) 202 PourPoint Temperature (° C.)   −7 Acid Value (mg KOH/gram)  23 Free FattyAcid (wt %)  11.5 Iodine value (gram I₂/100 grams) 118 Gardner Color  16Hydroxyl number (mg KOH/gram)  9

Example 2 Blowing the Corn Stillage Oil

Into a 2000 milliliter glass reactor equipped with a stirrer, a heatingmantel, a temperature regulator and air blowing tubes, 1200 grams ofcorn stillage oil, as indicated in Table 3, is charged. The cornstillage oil is heated to the temperatures indicated in Table 3. Air issparged through the oil as it is heated. The air is sparged through theoil at a rate that maximizes the rate while at the same time causes arelatively even distribution of air bubbles within the oil. The rate ofsparging is generally limited by the volume of the reactor. The speedwith which viscosity increases is directly proportional to the rate atwhich air is being blown into the corn stillage oil, and indirectlyproportional to the size of the air bubbles. The smaller the airbubbles, the more surface area the faster the reaction. The oil withinthe reactor is tested periodically to determine the viscosity at 40° C.of the blown oil. When the desired viscosity is obtained, the airsparging is stopped and the reactor is allowed to cool. Air is spargedthrough each of the samples for the times indicated in Table 3. Theproperties of the resulting blown oils are set forth in Table 3.

The properties of the resulting blown corn stillage oil are set forthbelow in Table 3.

TABLE 3 Properties of Blown Corn Stillage Oil Sample No. 3-1 3-2 3-3Corn Stillage Oil Used Sample Sample Sample 2-1 2-1 2-1a SpargingTemperature (° C.) 105 105 250 Sparging Time (hours)  23.5  42.5  14.5Viscosity @ 40° C. (cSt)  63 220 526 Viscosity @ 100° C. (cSt)  12  34.7 56 Viscosity Index 192 206 173 Flash Point (° C.) 284 277 295Saponification Value (mg KOH/gram) 190 200 192 Pour Point Temperature (°C.)   −9   −9   −4 Acid Value (mg KOH/gram)  21  23  21 Free Fatty Acid(wt %)  10.5  11.5  10.5 Iodine value (gram I₂/100 grams) 120 102  83Gardner Color  6  6 >18 Hydroxyl number (mg KOH/gram)  9  53  43

As can be seen from Table 3, varying the amount and temperature of thecorn stillage oil during sparging results in blown corn stillage oilhaving varying viscosities. The time required for blowing the cornstillage oils is relatively high, due to the large volume air bubblesutilized and the uneven dispersion of air bubbles within the reactor. Ahigher temperature was utilized to sparge Sample 3-3 to reduce thesparging time. If air was dispersed more evenly into the oil and thevolume of the air bubbles was smaller, the temperature to manufacture ablown corn stillage oil having a similar viscosity as sample, 3-1 wouldpreferably be reduced to between 105° C. and 115° C. With betterdispersion of air bubbles within the corn stillage oil and smaller airbubbles, the required sparging time to produce samples havingviscosities similar to those set forth in Samples 3-1 through 3-3, wouldbe greatly reduced.

In addition, while not measured, the blown corn stillage oils of Table 3are believed to contain less than one percent by weight titre.

Example 3 Stripping the Blown-Corn Stillage Oil

Into a 2000 glass reactor equipped with a stirrer, a heating mantel, atemperature regulator, a distillation column and a vacuum attachment1200 grams of the blown corn stillage oil as indicated in Table 4 ischarged. The blown corn stillage oil is stirred and a vacuum is drawn onthe reactor (50 torr or less) and the reactor is heated to 250° C. Thereactor is maintained under the vacuum at 250° C. to distill off freefatty acids and other low molecular weight components. The oil withinthe reactor is periodically tested for acid value. Once the acid valueof the oil reaches the values indicated in Table 4, the stripping isceased and the blown, stripped corn stillage oil is allowed to cool toambient temperature. The properties of the resulting Blown, StrippedCorn Stillage Oil are set forth below in Table 4.

TABLE 4 Properties of Blown, Stripped Corn Stillage Oil Sample No. 4-14-2 4-3 Blown Corn Stillage Oil Used 3-1 3-2 3-3 40° C. Viscosity (Pa ·s)  64 220 750 100° C. Viscosity (Pa · s)  13  34.7  70 Viscosity Index210 206 171 Flash Point (° C.) 293 298 323 Saponification Value (mgKOH/gram) 190 194 199 Pour Point Temperature (° C.) −10 −14   −6 AcidValue   <5  4.5  3.8 Free Fatty Acid (wt %)   <2.5  2.2  1.9 Iodinevalue (gram I₂/100 grams) 120 102  83 Gardner Color  10  11 >18 HydroxylValue  11  31  10 Stripping Time (hours)  1.5  1.5  1.0

The blown, stripped corn stillage oil of Sample 3-1 can be effectivelyused in general de-dust and lubrication end-use applications, such asbar and chain oil applications. The oil of Sample 3-2 exhibits a pourpoint temperature of −14° C. and will be effective for use in low pourpoint applications. The blown, stripped corn stillage oil of Sample 3-1with its relatively high flash point temperature and relatively highvalues of viscosity at 40° C. and 100° C. will be highly effective forend-use applications requiring high flash points.

In addition, while not measured, the blown, stripped corn stillage oilsof Table 4 are believed to contain less than one percent by weighttitre.

What is claimed is:
 1. A method for producing a high viscosity, lowvolatiles blown-corn stillage oil, the method comprising the steps of:(a) obtaining a corn stillage oil; (b) heating the oil to at least 90°C.; (c) passing air through the heated oil to produce a blown-cornstillage oil having a viscosity of at least 50 cSt at 40° C.; and (d)stripping the blown-corn stillage oil to reduce the acid value of theblown-corn stillage oil to 5 mg KOH/g or less.
 2. The method of claim 1,wherein the blown-corn stillage oil from step (d) exhibits a viscosityat 40° C. of at least 60 cSt and a viscosity at 100° C. of at least 11cSt.
 3. The method of claim 1 wherein the blown-corn stillage oil fromstep (c) exhibits a viscosity at 40° C. of at least 55 cSt and aviscosity at 100° C. of at least 11 cSt.
 4. A high viscosity, lowvolatiles blown, stripped corn stillage oil exhibiting: a viscosity at40° C. of at least 60 cSt; a viscosity at 100° C. of at least 12 cSt; anacid value of 4 mg KOH/gram or less; a hydroxyl number of from about 10to about 50; and a flash point of at least 275° C.
 5. The oil of claim4, wherein the oil exhibits a flash point of at least 290° C.
 6. A highviscosity, low volatiles blown, stripped corn stillage oil exhibiting: aviscosity at 40° C. of at least 700 cSt; a viscosity at 100° C. of atleast 63 cSt; an acid value of 3.5 mg KOH/gram or less; a hydroxylnumber of from about 10 to about 50; and a flash point of at least 310°C.
 7. The oil of claim 6, wherein the oil exhibits: a viscosity at 40°C. of at least 730 cSt; a viscosity at 100° C. of at least 68 cSt; anacid value of 3.0 mg KOH/gram or less; and a flash point of at least315° C.
 8. The oil of claim 6, wherein the oil exhibits a flash point ofat least 320° C.
 9. The oil of claim 6, wherein the oil exhibits an acidvalue of 2.8 mg KOH/gram or less.
 10. A method for producing a highviscosity, low volatiles blown-corn stillage oil, the method comprisingthe steps of: (a) obtaining a corn stillage oil; (b) heating the oil toat least 90° C.; (c) passing air through the heated oil to produce ablown-corn stillage oil; and (d) stripping the blown-corn stillage oilto reduce the acid value of the blown-corn stillage oil to 3.5 mgKOH/gram or less, wherein, the oil from step (d) has a flash point of atleast 310° C. and exhibits a viscosity of at least 680 cSt at 40° C. anda viscosity of at least 63 cSt at 100° C.
 11. The method of claim 10,wherein the blown-corn stillage oil from step (c) has a viscosity of atleast 650 cSt at 40° C. and a viscosity of at least 60 cSt at 100° C.12. The method of claim 10, wherein the corn stillage oil from step (d)has a viscosity of at least 730 cSt at 40° C. and a viscosity of atleast 68 cSt at 100° C.
 13. The method of claim 10, wherein the oil fromstep (d) has a flash point of at least 315° C.
 14. The method of claim10, wherein the oil from step (d) has a flash point of at least 320° C.15. The method of claim 10, wherein the oil from step (d) has an acidvalue of 3.0 mg KOH/gram or less.
 16. The method of claim 10, whereinthe oil from step (d) has an acid value of 2.8 mg KOH/gram or less. 17.The method of claim 1 wherein the oil from step (d) has a pour point of−13° C. or less.
 18. The method of claim 1, wherein the oil from step(d) has a pour point of −14° C. or less.
 19. A method for producing ahigh viscosity blown-corn stillage oil, the method comprising the stepsof: (a) obtaining a corn stillage oil; (b) heating the oil to at least105° C.; and (c) passing air through the heated oil to produce ablown-corn stillage oil having a viscosity of at least 50 cSt at 40° C.20. The method of claim 19, wherein the blown corn stillage oil has aviscosity of at least 60 cSt at 40° C.
 21. The method of claim 19,wherein the blown corn stillage oil has a viscosity of at least 130 cStat 40° C.
 22. The method of claim 19, wherein the blown corn stillageoil has a viscosity of at least 5000 cSt at 40° C.
 23. The method ofclaim 19, wherein the corn stillage oil comprises from 8 percent byweight to 16 percent by weight free fatty acids and the blown-cornstillage oil has at most 20 relative percent more free fatty acids thanthe corn stillage oil of step (a).
 24. The method of claim 19, whereinthe blown-corn stillage oil has at most 10 relative percent more freefatty acids than the corn stillage oil of step (a).
 25. The method ofclaim 19, wherein the blown-corn stillage oil has equivalent free fattyacids as the corn stillage oil of step (a).
 26. The method of any ofclaim 1, wherein a time required to pass air through the corn-stillageoil in step (c) to obtain a blown-corn stillage oil having a particularviscosity at 40° C. is shorter than the time required to manufacture ablown soybean oil having equivalent viscosity under the same temperatureand pressure conditions utilizing the same rate of passing air throughthe blown soybean oil as utilized for the blown corn stillage oil. 27.The method of claim 26, wherein the time required to obtain theblown-corn stillage oil is 25% less than the time to obtain theblown-soybean oil.
 28. The method of claim 1, wherein air is spargedthrough the corn stillage oil in step (c) at a rate of from about 0.009to 0.011 cubic feet per minute per pound oil.
 29. The method of claim10, wherein the blown-corn stillage oil from step (c) has a viscosity ofat least 150 cSt at 40° C.
 30. The method of claim 10, wherein theblown-corn stillage oil from step (c) has a viscosity of at least 200cSt at 40° C.